Dyeing of textile material



2,991,144 DYEING F TEXTILE MATERIAL John J. Sandilands, Saugus, Mass., and John H. 'Gormley,

Cranston, R.I., assignors to The Organic Chemical Corporation, a corporation of Rhode Island NoDrawing. Filed Aug. 28, 1958, Ser. No. 757,674 4 Claims. (Cl. 841) This invention relates to the dyeing of a textile fiber more particularly wool either in fabric or yarn form.

Heretofore in order to produce a fast black dye on W001 fiber, the time required was in excess of 3 hours usually about 3 /2 hours. For example, if 100 pounds of Wool were to be dyed with a monoazo mordant black dye, Color Index number 14645 as published in the volumes entitled Color 'Index, second edition, 1956, the dye bath would first be set by adding to 2500 pounds of water 5 pounds of acetic acid 56 Baum and 8 pounds of color. After the dye or color is dissolved, the 100 pounds of wool is put in and the kettle would be brought to a boil in 45 minutes and boiled 30 minutes and then 5 pounds acetic acid of 56 Baum would be added and boiled 30 minutes more then if the dye bath was not clear of color, 5 pounds acetic acid 56 Baum would be again added and the bath would be boiled for 30 minutes. At this point 2 pounds of sodium bichromate Na Cr O- .2H O will be added to develop the color and the whole will be boiled for 45 to 60 minutes and then the work will be washed clean. The total time will be approximately 3 /2 hours.

It has been discovered that the time for dyeing may be materially shortened and less acetic acid used if sulfamic acid is used with the dye according to the following:

EXAMPLE 1 Ingredients 100 lbs. wool either fabric or yarn in 2500 lbs. of water 8 lbs. color mixture comprising:

4.8 lbs. monoazo-rnordant-black, Color Index 14645,

167% strength 1.6 lbs. sulfamic acid 1.6 lbs. sodium sulfate EXAMPLE 2 Ingredients 100 lbs. wool in 2500 lbs. of water 8 lbs. color mixture comprising:

6 lbs. monoaZo-rnordant-black, Color Index 14645,

167% strength 2 lbs. sulfarnic acid EXAMPLE 3 Ingredients 100 lbs. wool in 2500 lbs. of water 8 lbs. color mixture comprising:

4.8 lbs. monoazo-mordant-black, Color Index 14645,

165% strength 2.4 lbs. sulfamic acid .8 lbs. sodium sulfate EXAMPLE 4 Ingredi nts 100 lbs. wool in 2500 lbs. of water 10 lbs. color mixture comprising:

8 lbs. monoazo-mordant-black, Color Index 14645,

100% strength 2 lbs. sulfamic acid The amount of water in the above examples is not critical and may be varied with 2000 to 3500 lbs, or more.

In Examples 1 and 3 one pound acetic acid 56 Baum is added to the water and raised to 140 F., and then the color mixture is added and after dissolved, the wool is introduced and the temperature will be raised to a boil as fast as possible which will be about 10 minutes. Boiling will continue at about 200 F. for another 10 minutes and then the bath will cool back to about 180 F. in ten minutes. 2 pounds of sodium bichromate Na Cr O .2H O will then be added and then the bath will be brought to a boil and boiling will continue for 10 minutes. It will then be cooled back to 140 F. for another tenminutes. The Wool work will be removed and washed. The total time will be 1 hour and 15 minutes or less than half of the time in the usual method as above recited where no sulfamic acid is used.

In Examples 2 and 4 two pounds of formic acid 85 Baum and two pounds acetic acid 28 Baum is added to the water and raised to 140 F., and then the color mixture is added and after dissolved, the wool is introduced and the temperature will be raised to a boil as fast as possible which will be about 10 minutes. Boiling will continue at about 200 F. for another 10 minutes and then the bath will cool back to about 180 F. in ten minutes. 2 pounds of sodium bichromate will then be added and then the bath will be brought to a boil and boiling will continue for ten minutes. It will then be cooled back to 140 F. for another ten minutes. The wool work will be removed and washed. The total time will be 1 hour and 15 minutes or less than half of the time in the usual method as above recited where no sulfamic acid is used.

The monoazo-mordant-black dye, Color Index 14645 above referred to is a solid and is available in different strengths such as 100% and 167% strength and also the sulfamic acid is a solid. We have found that the dry weights of parts of dye of 167% and 25 parts of sul-famic acid where a 68% dye compared to the weight of the Wool to be dyed is going to be used is satisfactory or parts of dye 100% and 20 parts of sulfamic acid where 10% dye is used is satisfactory. This range might be varied from 60 to 80 parts of color 167% with a corresponding 40 to 20 parts by weight of sulfamic acid or a variation 65 to parts of color 100% with a corresponding 35 to 15 parts by weight of sulfamic acid. The dyers usually like to use 6-8% of a dye and this proportion of 75% dye and 25% sulfamic acid mixed together allows them to use 6-8% of this mixture in a usual manner. We have found that if we use 60% of dye and 20% sulfamic acid and 20% sodium sulfate or 60% dye 30% sulfamic acid and 10% sodium sulfate that a very good mixture is provided and by using 68% of the mixture to wool weight, we get the same color effect on the fabric or wool as by using the color or dye alone and at a much reduced expense and in less time.

-In preparing the mixture of dye and sulfamic acid for addition to the kettle in which the wool to be treated is, 50 pounds will be placed in substantially 50 gallons of water and brought to a boil for several minutes until it is completely dissolved before a part equivalent to the percentage of dry mixture to the weight of the wool is taken from such a solution and added to the dye kettle.

It is found that if the proportion of dye and sulfamic acid are in a ratio of dye 167% to 10 sulfamic that the depths of color which are desired are not produced.

However with the 75-25 or 80-20 or 60-20-20 or 60-30-10 of dye and other materials the time saving.

is cut in half and the wool has a better feel than it has had with the process above first mentioned which lacks the sulfamic acid.

3 The precise chemical action which takes place is not definitely known but it is thought that the dye stuff ionizes in water as follows:

and when sulfamic acid is also present in the water, this monoazo mordant becomes an acid rather than a sodium salt and that this acid or acid salt is more soluble than the sodium salt.

There is a strong possibility of hydrogen bonding which would increase the solubility. There is also a possibility of hydrogen bonding between the nitro group of the dye and the ammonia group which is formed by the sulfamic acid. If some hydrogen bonding takes place at each possible point, it could multiply and could greatly increase the ionization and, therefore, the solubility.

The effect of the sulfamic acid on the sodium dichromate would make the chromate acid salt instead of a sodium salt. If an excess of acid is present, then polyacids may be formed as H Cr O Further theorizing, the nitrogens N of the diazo group provide two (2) electrons which are capable of drawing to them these two (2) hydrogens of the hydroxy groups of the naphthol rings:

They sort of half react with them so that the hydrogens are shared by the oxy'gens and the nitrogens. This results in somewhat of a ring formation which we believe is known to form in such cases:

Phenol ionizer:

and is a weak acid. This ring formation would lessen ionization of this type by the OH groups of the color. When you add a strong acid such as sulfamic, the H 63 from the acid (H NSO H) would stop this ring formation by attaching to the diazo nitrogens as follows:

ii i NaOaS N=N This would then allow the two (2) OH groups to ionize as phenol does, thus increasing the solubility of the color.

If the above theory is correct, then it is assumed that the same desirable results will be obtained by using sulfamic acid with all mordant dyes, although these have not been tried out, and we are not positive until trial that this holds true and in this list of mordant dyes which should work we include:

Azo mordant Diazo mordant Monoazo Anthraquinone mordant Pyrazolone diazo mordant Xanthrene mordant Triphenyl methan mordant Oxazine mordant Extremely soluble salts are formed by this procedure which causes the wool fiber to be dyed or penetrated very rapidly and when sulfamic acid is used with bichromate of soda to form a color lake with the above dye stufi very rapid color lake formation takes place inside of Wool or animal fibers. Further theorizing on the above it would appear that other metals which may be used with dye stuffs in place of the chromium may be used to perform this process, such metals being aluminum and cobalt. Any of the metals which may be used and have heretofore been used with mordant dyes could be used in this process by substitution for the chrome.

We claim:

1. In the process of dyeing, reducing the time of treating Wool with a monoazo mordant dye Color Index 14645 by incorporating in the dye bath with said dye, sulfamic acid in a quantity with relation to the weight of the dye based on 167% strength of from 20 to 40 percent.

2. In the process of dyeing, reducing the time of treating wool with a monoazo mordant dye Color Index 14645 by incorporating in the dye bath with said dye, sulfamic acid in a quantity with relation to the weight of the dye based on 167% strength of 20 to 30 percent and 20 to 10 percent filler.

3. In the process of dyeing parts by weight of wool in from 2000 to 3500 parts of water using 6 to 8 parts of a mixture of 60-70 parts monoazo mordant dye Color Index 14645 based on 167% strength and 20- 30 parts sulfarnic acid dry weight and 20-10 parts of sodium sulfate at the time of introduction of a metal to deposit the combined metal and dye on the wool.

4. In the process of dyeing 100 parts by weight of wool in from 2000 to 3500 parts of water using 6 to 8 parts of a mixture of 65-75 parts monoazo mordant dye Color Index 14645 based on 167% strength and 35-25 parts sulfamic acid dry weight at the time of introduction of a metal to deposit the combined metal and dye on the wool.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES The Colour Index, vol. 1, 2nd ed., 1956, p. 1590.

Diserens: Chem. Technology of Dyeing and Printing, vol. 1, 1948, N.Y., pp. 458-462.

UNITED STATES PATENT. OFFICE D CERTIFICATE OF CORRECT-ION 4 Patent No, 2,991,144 July 4 1961 John J. Sandilands et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 4 to 8 10 to 14, 20 to 24,, and 26 to 30 for that portion of each formula reading OH .OH

-N:N "N:N

read

:Signed and sealed this 27th day of March 1962,

(SEAL) Attest:

ERNESTW. SWIDER 1 DAVID L. LADD Attesting Officer Commissioner of Patents 

1. IN THE PROCESS OF DYEING, REDUCING THE TIME OF TREATING WOOL WITH A MONOAZO MORDANT DYE COLOR INDEX 14645 BY INCORPORATING IN THE DYE BATH WITH SAID DYE, SULFAMIC ACID IN A QUANTITY WITH RELATION TO THE WEIGHT OF THE DYE BASED ON 167% STRENGTH OF FROM 20 TO 40 PERCENT. 